CN102249286B

CN102249286B - Method for preparing zinc oxide micron sphere

Info

Publication number: CN102249286B
Application number: CN 201110160877
Authority: CN
Inventors: 王明松; 宋娟; 唐丽永
Original assignee: Jiangsu University
Current assignee: Jiangsu University
Priority date: 2011-06-16
Filing date: 2011-06-16
Publication date: 2013-05-08
Anticipated expiration: 2031-06-16
Also published as: CN102249286A

Abstract

The invention relates to a method for preparing a semiconductor oxide nano material, in particular to a method for preparing a zinc oxide micron sphere. In the method, ultrasonic activation treatment is not needed, the pH value of solution is adjusted and the appearance of a product is controlled by using NH4F, the solution is not needed to be diluted and the yield can be improved to the maximum extent; and the solution is not needed to be stirred in the water bath heat preservation process, the temperature of heat preservation can much lower than the boiling point of water, and the method contributes to large scale industrial production.

Description

A kind of preparation method of zinc oxide micron sphere

Technical field

The present invention relates to conductor oxidate preparations of nanomaterials method, be specifically related to a kind of preparation method of zinc oxide micron sphere.

Background technology

zinc oxide (ZnO) is a kind of novel I I-VI family semiconductor material with wide forbidden band, nontoxicity, and raw material is cheap and easy to get, has excellent photoelectricity, piezoelectricity and dielectric characteristics, nano-ZnO can be widely used as gas sensitive, catalytic material, anti-biotic material and photoelectric material etc., therefore become the popular research material in nanometer field over past ten years in the world, nano-ZnO is as air-sensitive, during photocatalyst material, require it to have large as far as possible specific surface area, to increase the contact area of ZnO and medium, thereby improve the sensitivity of gas sensor or strengthen photocatalysis effect, the ZnO nano sheet of the approximately tens of nanometers of thickness is a kind of nanostructures with bigger serface, yet in use reduce effective contact area of ZnO and medium due to the stack between nanometer sheet self, if the autonomous dress of nanometer sheet can be a kind of ball-like structure, can keep the independence between each nanometer sheet, and can effectively overcome the reunion between ball and ball, it will be a kind of desirable large-specific surface area nano structure, can be used for air-sensitive, the field such as photochemical catalysis and dye sensitization solar battery, relevant nanometer sheet builds the preparation of ZnO micron ball and only has a small amount of report, for example Chinese patent (CN 101249979 B) has been reported a kind of normal pressure water-bath preparation method of prickly sphere zinc oxide, this water-bath synthesis method needs the ultrasonic activation pre-treatment, solution needs thin up (efficient is low), bath temperature will reach boiling point and need and stir, offer in a separate paper (Journal of Crystal Growth 282 (2005) 165 – 172) and reported similar ZnO nano-structure, its preparation method adopts the solvent-thermal method take dehydrated alcohol as medium, solvent temperature is up to 190 ℃.

Summary of the invention

The object of the present invention is to provide a kind of nanometer sheet to build the low temperature water-bath preparation method of ZnO micron ball, need not ultrasonic activation, stirring, the method energy consumption is little, equipment simple, need not solvent, productive rate is high, good reproducibility, be easy to suitability for industrialized production.

For achieving the above object, in technical scheme of the present invention, adopt the standby nanometer sheet of low temperature water-bath legal system to build the ZnO micron ball.

Above-mentioned a kind of nanometer sheet builds the preparation method of ZnO micron ball, and concrete steps are:

1, the preparation of mixing solutions: with a certain amount of zinc salt, alkali and NH ₄F is dissolved in respectively distilled water, and mentioned solution is mixed, stirs, and makes mixed solution;

2, water bath heat preservation: with the standing insulation 10 ~ 24 hours in the water-bath of 60 ℃ ~ 100 ℃ of the mixed solution that makes;

3, cleaning-drying: will be through the solution filter of water bath heat preservation, the cleaning and filtering thing, dry at 30 ℃ ~ 60 ℃ temperature.

In above-mentioned preparation method, in step 1, zinc salt is Zn (NO ₃) ₂, Zn (CH ₃COO) ₂, ZnSO ₄, ZnCl ₂In a kind of; Alkali is a kind of in NaOH, KOH.

In above-mentioned preparation method, in step 1, the mol ratio of zinc salt and alkali is 0.1 ~ 0.3, NH ₄The mol ratio of F and alkali is 0.5 ~ 0.75.

Compared with the prior art, the invention has the advantages that:

Need not ultrasonic activation processes; With NH ₄F regulator solution pH value is also controlled the product pattern, and solution need not dilution, can improve to greatest extent productive rate; In the water bath heat preservation process, solution need not to stir, and holding temperature can far below the boiling point of water, be convenient to large-scale industrial production.

Description of drawings

Fig. 1 is the scanning electron microscope diagram that the nanometer sheet of embodiment 1 preparation builds the ZnO micron ball;

Fig. 2 is the EDS energy spectrum analysis figure that the nanometer sheet of embodiment 1 preparation builds the ZnO micron ball;

Fig. 3 is the scanning electron microscope diagram that the nanometer sheet of embodiment 2 preparations builds the ZnO micron ball;

Fig. 4 is the scanning electron microscope diagram that the nanometer sheet of embodiment 3 preparations builds the ZnO micron ball;

Fig. 5 is the scanning electron microscope diagram that the nanometer sheet of embodiment 4 preparations builds the ZnO micron ball.

Embodiment

The following examples are to further illustrate of the present invention, rather than limit the scope of the invention.

Embodiment 1:

1:0.1:0.75 takes a certain amount of NaOH, Zn (NO in molar ratio ₃) ₂, NH ₄F is dissolved in respectively in distilled water; Mentioned solution is mixed, stirs, make mixed solution; With the standing insulation 10 hours in the water-bath of 70 ℃ of the mixed solution that makes; Will be through the solution filter of water bath heat preservation, the cleaning and filtering thing, drying can obtain nanometer sheet and build the ZnO micron ball at the temperature of 40 ℃; By shown in Figure 1, thick approximately 20 nm of nanometer sheet sheet, sphere diameter 1 ~ 4 μ m of the zinc oxide micron sphere that is built into, Fig. 2 is the EDS energy spectrum analysis of this sample, does not detect impurity element, shows that prepared nanometer sheet builds the ZnO micron ball and has very high purity.

Embodiment 2:

1:0.15:0.6 takes a certain amount of NaOH, ZnSO in molar ratio ₄, NH ₄F is dissolved in respectively in distilled water; Mentioned solution is mixed, stirs, make mixed solution; With the standing insulation 15 hours in the water-bath of 80 ℃ of the mixed solution that makes; Will be through the solution filter of water bath heat preservation, cleaning and filtering thing, the dry ZnO micron ball that can obtain the nanometer sheet structure at the temperature of 50 ℃; As shown in Figure 3, thick approximately 20 nm of nanometer sheet, the sphere diameter of micron ball is 1.5 ~ 4 μ m approximately.

Embodiment 3:

1:0.15:0.6 takes a certain amount of KOH, ZnCl in molar ratio ₂, NH ₄F is dissolved in respectively in distilled water; Mentioned solution is mixed, stirs, make mixed solution; With the standing insulation 10 hours in the water-bath of 90 ℃ of the mixed solution that makes; Will be through the solution filter of water bath heat preservation, the cleaning and filtering thing, drying can obtain nanometer sheet and build the ZnO micron ball at the temperature of 40 ℃; As shown in Figure 4, thick approximately 20 nm of nanometer sheet sheet, the sphere diameter of micron ball is 1.5 ~ 4 μ m approximately.

Embodiment 4:

1:0.2:0.5 takes a certain amount of NaOH, Zn (CH in molar ratio ₃COO) ₂, NH ₄F is dissolved in respectively in distilled water; Mentioned solution is mixed, stirs, make mixed solution; With the standing insulation 24 hours in the water-bath of 60 ℃ of the mixed solution that makes; Will be through the solution filter of water bath heat preservation, the cleaning and filtering thing, drying can obtain nanometer sheet and build the ZnO micron ball at the temperature of 60 ℃; As shown in Figure 5, thick approximately 20 nm of nanometer sheet sheet sheet, sphere diameter is 1 ~ 2 μ m approximately.

Claims

1. the preparation method of a zinc oxide micron sphere, described zinc oxide micron sphere is built by nanometer sheet and forms, and it is characterized in that comprising the steps:

(1) preparation of mixing solutions: with zinc salt, alkali and NH ₄F is dissolved in respectively distilled water, and mentioned solution is mixed, stirs, and makes mixed solution, and the mol ratio of zinc salt and alkali is 0.1 ~ 0.3, NH ₄The mol ratio of F and alkali is 0.5 ~ 0.75;

(2) water bath heat preservation: with the standing insulation 10 ~ 24 hours in the water-bath of 60 ℃ ~ 100 ℃ of the mixed solution that makes;

(3) cleaning-drying: will be through the solution filter of water bath heat preservation, the cleaning and filtering thing, drying obtains zinc oxide micron sphere at 30 ℃ ~ 60 ℃ temperature;

In described step (1), zinc salt is Zn (NO ₃) ₂, Zn (CH ₃COO) ₂, ZnSO ₄Or ZnCl ₂Alkali is NaOH or KOH.